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US5900506A - Method of processing reaction mixtures obtained from the oxidation of cyclohexane - Google Patents

Method of processing reaction mixtures obtained from the oxidation of cyclohexane Download PDF

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Publication number
US5900506A
US5900506A US08/990,184 US99018497A US5900506A US 5900506 A US5900506 A US 5900506A US 99018497 A US99018497 A US 99018497A US 5900506 A US5900506 A US 5900506A
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Prior art keywords
cyclohexane
water
distillation
organic solvent
catalyst
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Expired - Lifetime
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US08/990,184
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English (en)
Inventor
Eric Fache
Philippe Leconte
Gilbert Marin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Fiber and Resin Intermediates SAS
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Rhone Poulenc Fiber and Resin Intermediates SA
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Assigned to R.P. FIBER & RESIN INTERMEDIATES reassignment R.P. FIBER & RESIN INTERMEDIATES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MARIN, GILBERT, FACHE, ERIC, LECONTE, PHILIPPE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/14—Adipic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

Definitions

  • the present invention relates to a method of oxidation of cyclohexane to adipic acid, and more particularly to the processing of the reaction mixtures obtained from this oxidation reaction.
  • Patent Application WO-A-94/07833 describes the oxidation of cyclic hydrocarbons into corresponding diacids, in a liquid phase containing a solvent, at a temperature of at least 60° C., using a gas containing oxygen and in the presence of an oxidation catalyst such as a cobalt compound, and points out that the solvent represents less than 1.5 mol per mole of cyclic hydrocarbon, that the said solvent comprises an organic acid having only primary or secondary hydrogen atoms and that the reaction is carried out in the presence of at least 0.002 mol of cobalt-based catalyst per 1,000 g of reaction mixture. At the end of the reaction, the diacid formed is isolated.
  • Patent Application W0-A-94/07834 filed on the same day as the one above, also describes the same process, but develops the phases of processing the final reaction mixture.
  • This processing consists in separating out the diacid formed, by cooling the reaction mixture in order to cause the said diacid to precipitate out, in separating by filtration the diacid from two liquid phases, a non-polar phase which is recycled, and a polar phase which is also recycled after an optional hydrolysis and separation of an additional amount of diacid.
  • the present invention provides a method of processing the reaction mixture obtained from the direct oxidation of cyclohexane to adipic acid with oxygen, in an organic solvent and in the presence of a catalyst, said method comprising:
  • the organic solvent is, more particularly, one or more aliphatic carboxylic acids.
  • the catalyst preferably contains cobalt, manganese or a mixture of cobalt and manganese.
  • the distillation is carried out such that most and, as far as is possible, essentially all, of the unconverted cyclohexane and the solvent, in particular the carboxylic acid preferably used, are separated from the adipic acid.
  • the method thus allows, in particular because of the distillation of the solvent and more particularly of the carboxylic acid solvent, the crystallization of the adipic acid to be performed in water, this solvent having many advantages over other crystallization solvents such as acetic acid, for example.
  • the lower solubility of adipic acid in cold water also makes it possible to limit or even, if this is economically acceptable, to dispense with the production of a second crop of less pure adipic acid from the solutions derived from the first crystallization.
  • additional risks of corrosion of the apparatus entailed by the prolonged presence of aliphatic carboxylic acid when this is used as solvent, are thus avoided.
  • the distillation step is generally carried out at a temperature of from about 25° C. to about 250° C. and at an absolute pressure of between about 10 Pa and atmospheric pressure.
  • the temperature of the mixture during the distillation will be maintained between about 70° C. and about 150° C.
  • the distillation can, if necessary, be carried out in several successive steps, in particular in the preferred mode in which it is desired to eliminate most, for example more than about 90% and even more than about 99%, of the solvent such as the aliphatic carboxylic acid.
  • the reaction mixture obtained from the direct oxidation of cyclohexane into adipic acid undergoes an operation of settling into two liquid phases before the distillation step: an upper, substantially cyclohexane phase and a lower phase substantially comprising the solvent, such as an aliphatic carboxylic acid, the diacids formed, the catalyst and some of the other reaction products.
  • the solvent such as an aliphatic carboxylic acid, the diacids formed, the catalyst and some of the other reaction products.
  • the cyclohexane phase is usually reintroduced into a cyclohexane oxidation operation, either directly or after optional processing consisting primarily in eliminating the water contained therein.
  • This processing can consist in particular of an azeotropic distillation.
  • the lower phase is subjected to the distillation mentioned above.
  • An advantageous variant of the method of the invention consists in introducing water vapor into the reaction mixture before or during the distillation step. This operation can allow better entrainment of certain compounds present in the mixture subjected to distillation. It can also carry out a partial or total hydrolysis of the carboxylic esters which may also be found in the mixture for distillation.
  • the distillate obtained in the distillation operation described above comprises the various volatile compounds and water. These volatile compounds can be upgraded and are thus recycled into a further cyclohexane oxidation reaction, after an at least partial elimination of water by any known means, in particular by azeotropic distillation.
  • the water added to the distillation residue represents from about 0.01 to about 5 times the weight of the mixture obtained after said distillation.
  • the amount of water added represents from about 0.1 to about 3 times this weight.
  • One variant of the method according to the invention consists in carrying out a liquid/liquid extraction on the aqueous solution obtained above, before crystallizing the adipic acid.
  • This extraction is performed using a water-immiscible solvent or mixture of solvents.
  • solvents such as aliphatic, cycloaliphatic or aromatic hydrocarbons such as, for example, hexane, cyclohexane, benzene and toluene, esters such as, for example, butyl acetate and cyclohexyl acetate, halogenated hydrocarbons such as, for example, trichloromethane and dichlorobenzenes, and ethers such as, for example, diisopropyl ether. Cyclohexane is preferably used, for its efficacy and so as not to complicate the process.
  • the cyclohexane layer separated from the reaction mixture by settling may be used for this liquid/liquid extraction, before the distillation step.
  • the cyclohexane solution obtained is usually reintroduced into a cyclohexane oxidation operation, either directly or, preferably, after processing consisting primarily in eliminating the water contained therein.
  • this processing can consist in particular of an azeotropic distillation.
  • Another variant of the process consists in heating the aqueous solution obtained after addition of water to the distillation residue, so as to hydrolyze the esters which may still be present in this solution.
  • the cyclohexanol formed by this hydrolysis is separated out by azeotropic distillation.
  • This hydrolysis can be performed in the presence of a strong acid catalyst which is either dissolved, such as a protonic acid, or not dissolved, such as an acidic heterogeneous catalyst.
  • the crystallization of the adipic acid from the aqueous solution is carried out according to the usual techniques of crystallization. It can be followed by recrystallization of the adipic acid obtained if the purity of the latter is not considered to be sufficient for the intended applications.
  • the aqueous solution remaining after crystallization of the adipic acid still contains a certain amount of dissolved adipic acid, which can be recovered in a second crop after concentrating the said aqueous solution. It also contains the other diacids formed in minor amount during oxidation of the cyclohexane, primarily glutaric acid and succinic acid, which can be separated out by known techniques, and, lastly, the catalyst.
  • the catalyst is generally recovered by liquid/liquid extraction or by membrane electrodialysis. The catalyst thus recovered is recycled in a further oxidation reaction of cyclohexane to adipic acid, after an additional amount has been added, if necessary.
  • the crude reaction mixture which is used in the method of the invention originates from the oxidation, which is known per se, of cyclohexane with a gas containing oxygen, in a liquid medium comprising an organic solvent, preferably a carboxylic acid, and in the presence of a catalyst, in particular a catalyst containing cobalt, manganese or a mixture of cobalt and manganese.
  • the initial cyclohexane/carboxylic acid weight ratio can be, for example, between about 0.1/1 and about 10/1 and preferably between about 0.2/1 and about 4/1.
  • the catalyst preferably comprises a cobalt compound which is soluble in the reaction medium, chosen, for example, from cobalt carboxylates (such as cobalt acetate tetrahydrate), cobalt chloride, cobalt bromide and cobalt nitrate and/or a soluble manganese compound chosen, for example, from manganese carboxylates (such as manganese acetate), manganese chloride, manganese bromide and manganese nitrate.
  • cobalt carboxylates such as cobalt acetate tetrahydrate
  • cobalt chloride such as cobalt bromide and cobalt nitrate
  • a soluble manganese compound chosen, for example, from manganese carboxylates (such as manganese acetate), manganese chloride, manganese bromide and manganese nitrate.
  • the amount of catalyst is generally between about 0.01% and about 5% and preferably between about 0.05% and about 2%, without these amounts being critical. However, an amount of catalyst having a sufficient activity should be used while not using excessively large amounts which will then need to be separated from the final reaction mixture and recycled.
  • the catalyst can also contain other compounds based on metals such as nickel and/or iron and/or copper and/or cerium and/or vanadium and/or hafnium and/or zirconium.
  • a compound for initiating the oxidation reaction such as, for example, a ketone or an aldehyde.
  • Cyclohexanone which is a reaction intermediate, is most particularly recommended.
  • the initiator represents from about 0.01% to about 20% by weight relative to the weight of the reaction mixture used, without these proportions having any critical value.
  • the initiator is especially useful when starting the oxidation and when cyclohexane is oxidized at a temperature below about 120° C. It can be introduced from the start of the reaction.
  • the carboxylic acid preferably used as solvent in the cyclohexane oxidation reaction is more particularly a saturated aliphatic carboxylic acid having from 2 to 9 carbon atoms and having only primary or secondary hydrogen atoms.
  • Acetic acid is preferably used as solvent for the cyclohexane oxidation reaction.
  • reference will occasionally be made, for the sake of convenience, to acetic acid as the carboxylic acid used in the various steps of the method.
  • the oxidation can also be carried out in the presence of water introduced from the initial stage of the method.
  • the cyclohexane oxidation reaction is generally carried out at a temperature of from about 60° C. to about 180° C. and preferably from about 70° C. to about 120° C.
  • the pressure is not a critical parameter of the reaction and is generally between about 10 kPa (0.1 bar) and about 10,000 kPa (100 bar).
  • the nitrogen pressure is brought to 20 bar, stirring is started at 1000 revolutions/min and the temperature is brought to 105° C. over 20 min.
  • the nitrogen is then replaced by 20 bar of depleted air (5% oxygen).
  • the inlet gas flow rate is adjusted to 250 liters/hour.
  • the oxygen titer at the reactor outlet remains less than 5% throughout the test.
  • the temperature in the autoclave varies between 104.9° C. and 105.1° C.
  • the decanter contains a two-phase mixture.
  • the upper, essentially cyclohexane phase, which contains few products and cobalt, is separated out.
  • the lower acetic phase (2164 g) contains most of the oxidation products and the cobalt.
  • the acetic phase is subjected to distillation under the following conditions:
  • the distillate represents 1860 g and the distillation residue about 300 g.
  • the cobalt catalyst is in the crystallization waters.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US08/990,184 1996-12-12 1997-12-12 Method of processing reaction mixtures obtained from the oxidation of cyclohexane Expired - Lifetime US5900506A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9615523 1996-12-12
FR9615523A FR2757155B1 (fr) 1996-12-12 1996-12-12 Procede de traitement de melanges reactionnels issus de l'oxydation du cyclohexane

Publications (1)

Publication Number Publication Date
US5900506A true US5900506A (en) 1999-05-04

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US08/990,184 Expired - Lifetime US5900506A (en) 1996-12-12 1997-12-12 Method of processing reaction mixtures obtained from the oxidation of cyclohexane

Country Status (17)

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US (1) US5900506A (id)
EP (1) EP0847980B1 (id)
JP (1) JP3197518B2 (id)
KR (1) KR100529204B1 (id)
CN (1) CN1071734C (id)
AR (1) AR009663A1 (id)
BR (1) BR9705515A (id)
CA (1) CA2222365C (id)
CZ (1) CZ397997A3 (id)
DE (1) DE69710301T2 (id)
FR (1) FR2757155B1 (id)
ID (1) ID19144A (id)
PL (1) PL323661A1 (id)
RU (1) RU2177937C2 (id)
SK (1) SK170097A3 (id)
TW (1) TW402589B (id)
UA (1) UA56135C2 (id)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6063958A (en) * 1998-12-22 2000-05-16 China Petrochemical Development Corporation Method of recovering adipic acid and 6-hydroxycaproic acid from waste solution of alkali metal salts of organic acids coming from the process of cyclohexane oxidation
WO2004041765A1 (fr) * 2002-10-30 2004-05-21 Rhodia Polyamide Intermediates Procede de fabrication d'acides carboxyliques
US6787669B1 (en) * 1998-03-05 2004-09-07 Rhodia Fiber & Resin Intermediates Method for separating and purifying adipic acid
CN102757332A (zh) * 2011-04-27 2012-10-31 中国石油化工集团公司 一种环己烷氧化产物的处理方法
CN118750888A (zh) * 2024-06-12 2024-10-11 重庆华峰化工有限公司 一种环己烷催化氧化法氧化液的分离系统及方法

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2784098B1 (fr) * 1998-09-14 2000-11-24 Rhone Poulenc Fibres Procede de separation et de cristallisation de l'acide carboxylique issu de l'oxydation directe d'un hydrocarbure
TW460452B (en) * 1998-09-14 2001-10-21 Rhodia Fiber & Amp Resin Inter Process for the crystallization of carboxylic acid and process for manufacturing crystalline carboxylic acid
FR2795720B1 (fr) * 1999-06-29 2003-05-02 Rhone Poulenc Fibres Procede de cristallisation d'acide carboxylique et procede de fabrication d'acide carboxylique cristallise
FR2784099B1 (fr) * 1998-09-14 2000-11-24 Rhone Poulenc Fibres Procede de separation et de purification de l'acide carboxylique issu de l'oxydation directe d'un hydrocarbure
FR2796377A1 (fr) * 1999-07-16 2001-01-19 Rhone Poulenc Fibres Procede de fabrication d'acide carboxylique cristallise
JP5345266B2 (ja) * 2000-08-18 2013-11-20 株式会社ダイセル カルボン酸の製造方法
KR100398992B1 (ko) * 2001-05-02 2003-09-22 재원산업 주식회사 디메틸 아디페이트 증류방법
US6946572B2 (en) * 2003-10-16 2005-09-20 Invista North America S.A.R.L. Crystallization of adipic acid from its solution in aqueous nitric acid
CN1936586B (zh) * 2006-09-15 2010-05-12 北京工业大学 一种对空(氧)气氧化环己烷反应混合物进行全分析的方法
CN102924262A (zh) * 2011-08-10 2013-02-13 中国石油化工集团公司 己二酸的制备方法
CN112441904B (zh) * 2019-09-04 2023-04-07 中国石油化工股份有限公司 环己烷直接氧化法制己二酸工艺分离和母液回用的连续方法
CN114426472B (zh) * 2020-10-14 2024-03-26 中国石油化工股份有限公司 环己烷直接氧化制备己二酸的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1266886A (fr) * 1959-09-08 1961-07-17 Chemstrand Corp Perfectionnements apportés à la fabrication d'acide adipique
FR1477314A (fr) * 1965-04-28 1967-04-14 Ici Ltd Séparation des produits d'oxydation du mélange obtenu par oxydation du cyclohexane
US3607926A (en) * 1969-03-18 1971-09-21 Texaco Inc Dicarboxylic acid manufacture
US4052441A (en) * 1974-10-10 1977-10-04 Josef Klemens Brunner Separation of acids and esters in the processing of waste salt solution of cyclohexanone manufacture
WO1996003365A1 (fr) * 1994-07-21 1996-02-08 Rhone-Poulenc Fiber & Resin Intermediates Procede de recyclage du catalyseur dans l'oxydation directe du cyclohexane en l'acide adipique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1266886A (fr) * 1959-09-08 1961-07-17 Chemstrand Corp Perfectionnements apportés à la fabrication d'acide adipique
FR1477314A (fr) * 1965-04-28 1967-04-14 Ici Ltd Séparation des produits d'oxydation du mélange obtenu par oxydation du cyclohexane
US3607926A (en) * 1969-03-18 1971-09-21 Texaco Inc Dicarboxylic acid manufacture
US4052441A (en) * 1974-10-10 1977-10-04 Josef Klemens Brunner Separation of acids and esters in the processing of waste salt solution of cyclohexanone manufacture
WO1996003365A1 (fr) * 1994-07-21 1996-02-08 Rhone-Poulenc Fiber & Resin Intermediates Procede de recyclage du catalyseur dans l'oxydation directe du cyclohexane en l'acide adipique

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6787669B1 (en) * 1998-03-05 2004-09-07 Rhodia Fiber & Resin Intermediates Method for separating and purifying adipic acid
US6063958A (en) * 1998-12-22 2000-05-16 China Petrochemical Development Corporation Method of recovering adipic acid and 6-hydroxycaproic acid from waste solution of alkali metal salts of organic acids coming from the process of cyclohexane oxidation
WO2004041765A1 (fr) * 2002-10-30 2004-05-21 Rhodia Polyamide Intermediates Procede de fabrication d'acides carboxyliques
CN102757332A (zh) * 2011-04-27 2012-10-31 中国石油化工集团公司 一种环己烷氧化产物的处理方法
CN102757332B (zh) * 2011-04-27 2015-07-01 中国石油化工集团公司 一种环己烷氧化产物的处理方法
CN118750888A (zh) * 2024-06-12 2024-10-11 重庆华峰化工有限公司 一种环己烷催化氧化法氧化液的分离系统及方法

Also Published As

Publication number Publication date
CZ397997A3 (cs) 1998-06-17
FR2757155A1 (fr) 1998-06-19
CA2222365C (fr) 2001-10-23
DE69710301D1 (de) 2002-03-21
SK170097A3 (en) 1998-07-08
UA56135C2 (uk) 2003-05-15
CA2222365A1 (fr) 1998-06-12
CN1071734C (zh) 2001-09-26
EP0847980A1 (fr) 1998-06-17
RU2177937C2 (ru) 2002-01-10
FR2757155B1 (fr) 1999-11-12
JP3197518B2 (ja) 2001-08-13
PL323661A1 (en) 1998-06-22
KR100529204B1 (ko) 2006-04-21
JPH10175910A (ja) 1998-06-30
EP0847980B1 (fr) 2002-02-06
AR009663A1 (es) 2000-04-26
DE69710301T2 (de) 2002-10-10
TW402589B (en) 2000-08-21
CN1184804A (zh) 1998-06-17
BR9705515A (pt) 2000-05-02
KR19980064035A (ko) 1998-10-07
ID19144A (id) 1998-06-18

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